Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/40—Nickelates
  • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
  • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
  • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/44—Methods for charging or discharging
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to the general field of rechargeable sodium-ion (Na-ion) batteries.
• the invention relates more specifically to active materials of positive electrode for Na-ion batteries, and to positive electrodes comprising them.
• the invention also relates to a method for cycling Na-ion batteries.
• Na-ion batteries represent one of the most promising alternative solutions to lithium-ion batteries, sodium being more interesting than lithium economically, in particular because of its abundance and its low cost.
• Na-ion battery cell assemblies can only be considered as prototypes, since only tests have been carried out.
• the first category contains polyanionic compounds.
• the compound Na3V2 (P0 4 ) 2F3 has been identified as being suitable for use within Na-ion batteries. Indeed, it is characterized in particular by ease of synthesis, stability when used in wet conditions, or even high specific energy, as the document WO 2014/009710 describes it.
• the presence of vanadium within the electrode can be problematic during the use of the Na-ion battery in the medium / long term, given its toxic nature.
• the specific capacity of the latter is limited due to its relatively high molecular weight.
• the second category contains lamellar oxides of sodium.
• Na3V2 (P0 4 ) 2F3 (approximately 4.5 g / cm 3 vs approximately 3 g / cm 3 ).
• NaNio, 5Mno, 502 has a theoretical capacity of about 240 mAh / g, as described in the document "Study on the reversible electrode reaction of Nai-xNio.sMno.sCh for a rechargeable sodium ion battery", S. Komaba, N. Yabuuchi, T. Nakayama, A. Ogata, T. Ishikawa, I. Nakai, J. Inorg Chem. 5 1, 621 1 -6220 (2012). However, it turns out that the capacity of this material deteriorates during the charge and discharge cycles of the Na-ion battery.
• the subject of the invention is therefore an active material of a positive electrode for a sodium-ion battery of formula (I) below:
• x varies from 0.9 to 1;
• - y varies from 0.05 to 0.1;
• - z varies from 0.1 to 0.3.
• Another object of the invention is a process for preparing the active material according to the invention.
• the invention also has for its object and a positive electrode comprising the active material according to the invention.
• Another object of the invention is a Na-ion battery cell, comprising the electrode according to the invention.
• the invention also relates to a Na-ion battery comprising at least one cell according to the invention.
• the invention also relates to a particular cycling method for Na-ion batteries comprising an active material with a particular positive electrode.
• FIG 1 is a graph representing the capacity of a Naion battery cell, as a function of the number of charge and discharge cycles;
• FIG 2 is a graph representing the voltage of a Naion battery cell, as a function of capacity
• FIG 3 is a graph representing the capacity of a Naion battery cell, as a function of the number of charge and discharge cycles;
• FIG 4 is a graph representing the voltage of a Naion battery cell, as a function of capacity
• FIG 5 is a graph representing the voltage of a Naion battery cell, as a function of capacity
• FIG 6 is a graph representing the voltage of a Naion battery cell, as a function of capacity
• FIG 7 is a graph representing the voltage of a Naion battery cell, as a function of capacity
• FIG 8 is a graph representing the voltage of a half-cell of Na-ion battery, according to the capacity.
• Fe active material of positive electrode for Na-ion battery according to the invention corresponds to formula (I) as mentioned above.
• y varies from 0.06 to 0.1, preferably y is equal to 0.1.
• z varies from 0.2 to 0.3.
• x varies from 0.95 to 1, preferably x is equal to 1.
• the subject of the invention is also a process for preparing the active material according to the invention comprising the following steps:
• step (b) heating the mixture obtained at the end of step (a) to a temperature ranging from 800 to 1000 ° C;
• the compound is chosen from oxides.
• the oxide is chosen from NiO, CuO, M Cb, Mn0 2 , Ti0 2 and their mixtures.
• the precursor is sodium carbonate.
• an oxide chosen from NiO, CuO, Mn 2 ⁇ 3 , Mn0 2 , Ti0 2 and their mixtures is mixed with sodium carbonate.
• the mixture obtained at the end of step (a) is heated to a temperature ranging from 850 to 950 ° C.
• step (b) takes place over a period ranging from 6 hours to 20 hours, preferably from 9 hours to 15 hours, more preferably from 11 to 13 hours, more preferably from 12 hours.
• step (b) is followed by a cooling and drying step.
• the mixture is heated to 900 ° C in an oven for 12 hours, then cooled to 300 ° C, then removed from the oven.
• Another object of the invention is a positive electrode comprising the active material according to the invention.
• the positive electrode according to the invention further comprises at least one conductive compound.
• the conductive compound is chosen from metallic particles, carbon, and their mixtures, preferably carbon.
• Said metallic particles can be particles of silver, copper or nickel.
• the carbon can be in the form of graphite, carbon black, carbon fibers, carbon nanowires, carbon nanotubes, carbon nanospheres, preferably carbon black.
• the positive electrode according to the invention advantageously comprises the carbon black SuperC65® sold by Timcal.
• the content of active material according to the invention varies from 50 to 90% by weight, preferably from 70 to 90% by weight, relative to the total weight of the positive electrode.
• the content of conductive compound varies from 10 to 50% by weight, preferably from 10 to 30% by weight, more preferably from 15 to 25% by weight, relative to the total weight of the positive electrode.
• the present invention also relates to a battery cell
• Na-ion comprising a positive electrode comprising the active material according to the invention, a negative electrode, a separator and an electrolyte.
• the battery cell comprises a separator located between the electrodes and playing the role of electrical insulator.
• separators are generally composed of porous polymers, preferably polyethylene and / or polypropylene. They can also be made of glass microfibers.
• the separator used is a separator made of glass microfibers CAT No. 1823-070® sold by Whatman.
• said electrolyte is liquid.
• This electrolyte can comprise one or more sodium salts and one or more solvents.
• the sodium salt or salts may be chosen from NaPF6, NaCl0 4 , NaBF 4 , NaTFSI, NaFSI, and NaODFB.
• the sodium salt or salts are preferably dissolved in one or more solvents chosen from aprotic polar solvents, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and the methyl and ethyl carbonate.
• aprotic polar solvents for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and the methyl and ethyl carbonate.
• the electrolyte comprises propylene carbonate in admixture with the sodium salt NaPFô at 1 M.
• the present invention also relates to a Naion battery comprising at least one cell as described above.
• the present invention also relates to a method for cycling a sodium-ion battery comprising a negative electrode, a separator, an electrolyte and a positive electrode comprising an active material of formula (II) below:
• - r varies from 0.05 to 0.1;
• the upper voltage ranging from 4.2 to 4.7 V, preferably 4.4 to 4.6 V, more preferably equal to 4.5 V
• the lower voltage ranging from 0.5 to 2.5, preferably from 1.5 to 2.5, more preferably equal to 2 V
• the cycles being carried out at a cycling regime ranging from C / 20 to C, C denoting the cycling regime of the sodium-ion battery.
• a solid and stable layer called "Cathode Electrolyte Interphase” (CEI) more protective is generated, by compared to an application of a lower higher voltage, for example less than 4, IV.
• This IEC located between the cathode and the electrolyte, is an essential element for proper functioning Na-ion battery, because not only does it conduct sodium ions very well but it also has the advantage of stopping the catalytic decomposition of the electrolyte.
• the active material of formula (II) is of formula (I).
• the cycling regime is C / 10.
• the positive electrodes EN-A and EN-B are comparative electrodes.
• the electrodes EN-C to EN-F are electrodes according to the invention.
• the EN-A positive electrode is made by mixing 80% by weight of the active material A, which has been directly transferred to a glove box from the oven without exposure to air, and 20% by weight of the carbon black SuperC65® , the mixture then being ground for 30 minutes using a SPEX 8000M mixer.
• the other positive electrodes EN-B to EN-F are produced by mixing 80% by weight of the active material, respectively B to F, and 20% by weight of the carbon black SuperC65®, the mixtures then being ground in the same way as for the positive electrode EN-A.
• active materials B to F were transferred directly into a glove box from the oven without exposure to air.
• the cells were then prepared respectively comprising the positive electrodes EN-A to EN-F.
• the cells are respectively named CE-A, CE-B, CE-C, CE-D, CE-E and CE-F.
• the assembly of the electrochemical cells is carried out in a glove box using a device consisting of a button cell of the type 2032.
• Each of the cells comprises a separator, a negative electrode and an electrolyte.
• 1823-070® are used to avoid any short circuit between the positive electrode and the negative electrode during the charge and discharge cycles. These separators are cut to a diameter of 16.6 mm and a thickness of 400 qm.
• An electrode of 1 cm 2 is obtained by drilling hard carbon discs coated on a film with an aluminum current collector.
• the active material of hard carbon is approximately 5. 20 mg / cm 2 .
• the electrolyte used comprises a solution composed of 1 M
• Electrodes EN-B to EN-F A mass of 8.50, 9.35, 9.36, 9.35 and 8.75 mg of each of the electrodes EN-B to EN-F, respectively, in the form of a powder, is then spread over a aluminum sheet placed in cells CE-B to CE-F, respectively.
• the separators, negative electrodes and electrolytes are identical to those used in the CE-A cell.
• Galvanostatic cycling is carried out using a BioLogic cycler at a cycling speed of C / 20, C denoting the cell capacity, at voltages ranging from 4.2 to 1.5 V.
• CE-A was measured as a function of the number of cycles, as shown in Figure 1. The change in capacity is observed on curve A.
• a capacity of approximately 130 mAh.g 1 is measured after 30 cycles.
• Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
• curve B l corresponds to the first charge and discharge cycle.
• Curve B2 corresponds to the second charge and discharge cycle, and so on until curve B5 which corresponds to the fifth charge and discharge cycle.
• Galvanostatic cycling is carried out using a BioLogic cycler at a cycling speed of C / 20, C denoting the capacity of the cell, at voltages ranging from 4.4 to 1.2 V.
• the capacity of the CE-C cell was measured as a function of the number of cycles, as shown in FIG. 3. The evolution of the capacity is observed on curve C.
• the capacity of the CE-C cell according to the invention is higher and more stable over the charge and discharge cycles.
• the capacity of the cell comprising the active material according to the invention is improved.
• the voltage of the CE-C cell was measured as a function of the capacity, as shown in Figure 4.
• Curves C l to C5 are more linear than curves B l to B5.
• the degradation of the capacity of the CE-C cell is not observed as was the case for the CE-B cell. Indeed, the capacity of the CE-C cell is more stable.
• Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
• the voltage of the CE-D cell was measured as a function of capacity, as shown in Figure 5.
• Curves D l to D5 are more linear than curves B l to B5.
• CE-E cell according to the invention is a cell according to the invention
• Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
• the voltage of the CE-E cell was measured as a function of capacity, as shown in Figure 6.
• Curves E l to E5 are more linear than curves B l to B5.
• the degradation of the capacity of the CE-E cell is not observed as it was the case for the CE-B cell. Indeed, the capacity of the CE-E cell is more stable.
• Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
• the voltage of the CE-F cell was measured as a function of capacity, as shown in Figure 7.
• curve F l corresponds to the first charge and discharge cycle, and so on until curve F5 which corresponds to the fifth charge and discharge cycle.
• Curves F l to F5 are more linear than curves B l to B5.
• the degradation of the capacity of the CE-F cell is not observed as was the case for the CE-B cell. Indeed, the capacity of the CE-F cell is more stable.
• the positive electrode is made by mixing 80% by weight of the active material NaNio, 45Cuo, o5Mno, 4 Tio, i02, which was directly transferred into a glove box from the oven without exposure to air, and 20% by weight SuperC65® carbon black, the mixture then being ground for 30 minutes using a SPEX 8000M mixer.
• a half cell was then prepared comprising the above-mentioned positive electrode.
• the assembly of the half-cell is carried out in a glove box using a device consisting of a Swagelok® connector 12 mm in diameter.
• the half cell includes a separator, a negative electrode and an electrolyte.
• Two layers of CAT No. 1823-070® glass microfiber separator are used to prevent short circuits between the positive and negative electrodes during the charge and discharge cycles. These separators are cut to a diameter of 12 mm and a thickness of 500 qm.
• 11 mm diameter pellets are cut from a sodium metal sheet. The pellet obtained is then bonded by pressure on a stainless steel current collector. This collector is then deposited on the separating membrane in the cell.
• the electrolyte used comprises a solution composed of 1 M NaPFô dissolved in propylene carbonate.
• Electrochemical test A cycling process comprising applying a plurality of charge and discharge cycles at voltages ranging from 2 to 4.5V, was carried out, at a cycling rate of C / 10.
• the half-cell voltage was measured as a function of capacity, as shown in Figure 8.
• the curve G designates the plurality of charge and discharge cycles which has been carried out.
• the capacity of the half-cell is stable with the repetition of the charge and discharge cycles.

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• Inorganic Compounds Of Heavy Metals (AREA)

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• 2018
  • 2018-10-11 FR FR1859417A patent/FR3087299B1/fr active Active
• 2019
  • 2019-10-10 WO PCT/FR2019/052414 patent/WO2020074836A1/fr unknown
  • 2019-10-10 CN CN201980073913.7A patent/CN113454031A/zh active Pending
  • 2019-10-10 JP JP2021519643A patent/JP2022504568A/ja active Pending
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  • 2019-10-10 KR KR1020217014056A patent/KR20210116433A/ko unknown

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